Novel electrolyte for lithium ion batteries

ABSTRACT

A non-aqueous electrolyte usable in rechargeable lithium-ion batteries including a solution of LiPF 6 /carbonate based electrolytes with low concentrations of LiFOP such that the thermal stability is increased compared to a standard lithium battery. A method of making lithium tetrafluorophospahte (LiF 4 C 2 O 4 , LiFOP) including, reacting PF 5  with lithium oxalate, recrystallizing DMC/dichloromethane from a 1:1 mixture of to separate LiF 4 OP from LiPF 6  to form a lithium salt. An electric current producing rechargeable Li-ion cell. The rechargeable lithium ion cell includes an anode, a cathode, and a non-aqueous electrolyte comprising a solution of a lithium salt in a non-aqueous organic solvent containing lithium tetrafluorooxalatophosphate (LiPF 4 (C 2 O 4 ), LiF 4 OP).

PRIORITY INFORMATION

The present application is a continuation application of PCT/US08/56161, filed on Mar. 8, 2008 which claims priority from Provisional Patent Application 60/893,734 filed with the United States Patent and Trademark Office on Mar. 8, 2007.

GOVERNMENT SPONSORSHIP

The present invention was made with U.S. Government support under NSF/CIA (Award No. DMR-0442024) and the US Army Research Laboratory (Contract No. W911QX-07-C-0026 to Yardney Technical Products). The U.S. Government has certain rights to this invention.

BACKGROUND OF THE PRESENT INVENTION

Lithium ion batteries (LIBs) are one of the most widely used portable power sources. However, loss of power and capacity and upon storage or prolonged use especially at elevated temperature (>50° C.) limits the application of LIB for electric vehicle (EV) and hybrid electric vehicle (HEV) applications. The performance degradation is frequently linked to the thermal instability of LiPF₆ and the reactions of the electrolyte with the surface of the electrode materials. This has prompted the development of alternative electrolytes for lithium ion batteries.

The most widely utilized lithium salt for lithium ion batteries is lithium hexafluorophosphate (LiPF₆). However, LiPF₆ has poor thermal and hydrolytic stability and is thus not ideal. One of the most widely investigated “alternative” salts for lithium ion battery electrolytes is lithium bisoxalatoborate (LiB(C₂O₄)₂, LiBOB). Lithium ion batteries containing LiBOB based electrolytes have been reported to operate up to 70° C. with little capacity fade. However, the use of LiBOB has been limited by the poor solubility of LiBOB in common carbonate solvents and the poor performance of LiBOB electrolytes at low temperature. LiBOB based electrolytes have been reported to generate a stable solid electrolyte interface (SEI) on the surface of the anode due to ring-open reactions of the oxalate moiety and the formation of trigonal borates.

SUMMARY OF THE INVENTION

In an effort to develop new salts for lithium ion battery electrolytes, lithium tetrafluorooxalatophosphate (LiPF₄(C₂O₄), LiF₄OP) has been designed as a new compound. Upon discovery of this new and potentially interesting lithium salt, a synthetic method for the preparation of LiF₄OP was developed.

These and other features and objectives of the present invention will now be described in greater detail with reference to the accompanying drawings, wherein:

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a ¹⁹F, and ³¹P NMR spectra of LiF₄OP electrolyte;

FIG. 2 is a graph of the charge-discharge characteristics of coin cell containing 1:1 LiPF₆/LiF₄OP in 1:1:1 EC/DEC/DMC for the first four charge-discharge cycles;

FIG. 3 is a graph of the discharge capacity (Ah) of coin cell containing 1:1 LiPF₆/LiF₄OP in 1:1:1 EC/DEC/DMC during first four charge-discharge cycles;

FIG. 4 is a graph of the charge-discharge characteristics of coin cell containing 1 M LiPF₆ with 2% (wt) LiF₄OP in 1:1:1 EC/DEC/DMC for the first four charge-discharge cycles;

FIG. 5 is a graph of the discharge capacity (Ah) of coin cell containing 1 M LiPF₆ with 2% (wt) LiF₄OP in 1:1:1 EC/DEC/DMC during first four charge-discharge cycles;

FIG. 6 is a graph of the conductivity of a 1:1 mixture of LiPF₆/LiF₄OP vs LiPF₆ in a ternary mixture of carbonate solvents; and

FIG. 7 is a schematic of a lithium salt.

DETAILED DESCRIPTION OF THE INVENTION

Lithium tetrafluoro oxalato phosphate (LiPF₄(C₂O₄)) (as shown in FIG. 7) can be used as a lithium salt in the lithium battery. The salt has a high conductivity and solubility but is more thermally stable than the industry standard LiPF₆ which could lead to a longer calendar life performance.

Experimental

Battery grade carbonate solvents were obtained from EM Industries (located in Japan), LiPF₆ from Hashimoto Chemical Corporation (Japan, without further purification. Purity was verified by Nuclear Magnetic Resonance (NMR) spectroscopy. Samples for NMR spectroscopy were prepared in an Ar-filled glove box followed by flame sealing and stored for varying lengths of time at 85° C. NMR analyses were conducted on a JEOL 400 MHz NMR spectrometer. ¹H NMR resonances were referenced to EC at 4.51 ppm, ¹⁹F NMR resonances were referenced to LiPF₆ at 65.0 ppm and ³¹P NMR resonances were referenced to LiPF₆ at −145.0 ppm.

Lithium tetrafluorooxalatophosphate (LiF₄OP) was synthesized by the reaction of PF₅ gas, generated by heating solid LiPF₆ to 200° C., transferred via a slow stream of N₂ into a suspension of lithium oxalate in dimethyl carbonate at 25° C. The reaction mixture was allowed to stir at 25° C. for 3 h followed by purification by repeated recrystallization from 1:1 dimethyl carbonate/dichloromethane. An electrolyte composed of 1:1 LiPF₆/LiF₄OP in 1:1:1 ethylene carbonate (EC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) was examined in lithium-ion coin cells with LiNi_(0.8)Co_(0.2)O₂ and mesocarbon microbead (MCMB) graphite as cathode and anode materials respectively. The cells underwent four formation cycles (C/20 and three C/10).

TABLE 1 ¹⁹F, ³¹P and ¹¹B NMR assignments of Lithium hexafluoro phosphate and lithium tetrafluorooxalatophosphate ¹⁹F ppm (mult, ³¹P ppm ¹¹B Salts J_(P-F) or J_(B-F)) (mult, J_(P-F)) ppm LiPF₆ 65.0 (d, 709) −145.0 — (sept, 709) LiF₄OP 79.5 (d-t 776, 52) −142.2 (t-t — 62.7 (d-t 748, 52) 776, 748)

Preparation and Investigation of LiF₄OP

A 1:1 mixture of LiF₄OP and LiPF₆ was prepared by the reaction of PF₅ with lithium oxalate (See Scheme 1). Repeated recrystallization from a 1:1 mixture of DMC/dichloromethane can be used to remove LiPF₆. An investigation of the thermal stability of carbonate solutions of LiF₄OP and the use of 1:1 LiPF₆/LiF₄OP in 1:1:1 EC/DMC/DEC as an electrolyte in lithium ion batteries was conducted. Dissolution of LiF₄OP in 1:1:1 EC/DEC/DMC resulted in a clear colorless solution. ¹⁹F and ³¹P NMR spectroscopy confirmed the structure of LiF₄OP (FIG. 2). Thermal stability of 1.0 M LiF₄OP in EC:DEC:DMC (1:1:1) was investigated by NMR spectroscopy. Storage of the electrolyte at 85° C. for 3 months resulted in a slight yellowing of the solution, likely due to trace impurities, but no evidence for bulk electrolyte decomposition. The ¹H, ¹⁹F, and ³¹P NMR spectra of the electrolyte revealed that a low concentration of the lithium fluorophosphate (OPF₂(OLi)) was generated during the first 48 hours of storage at 85° C. However, the concentration of OPF₂(OLi) did not increase upon storage for 3 months at 85° C. Incorporation of additive concentrations of LiF₄OP to LiPF₆ based electrolytes was investigated. The addition of 2% (wt) LiF₄OP to ternary electrolyte inhibited the thermal decomposition of the electrolyte.

Performance of Lithium-Ion Cells with 1:1 LiPF₆/LiF₄OP

The effect of LiF₄OP on the initial cycling performance of coin cells was examined. The cells were cycled in the following schedule: four formation cycles (one at C/20 followed by three C/10 charge-discharge rate cycles) at 25° C. FIG. 3 is a representative data set of the charge-discharge characteristics of a coin cell containing 1:1 LiPF₆/LiF₄OP (1 M Li) in EC:DEC:DMC (1:1:1). The data suggested that the LiF₄OP electrolyte had good performance in LIB. Compared to cells containing ternary electrolyte, a plateau around 1.9 V was clearly observed during the first cycle due to the reduction of oxalate impurities in LiF₄OP. As with previous investigations with LiBOB electrolytes, the size of the 1.9 V plateau was dependent upon the concentration of LiF₄OP in LiPF₆. Cells containing 1:1 LiPF₆/LiF₄OP in 1:1:1 EC/DEC/DMC had good reversibility over the first four cycles, FIG. 4, suggested that LiF₄OP electrolytes were not detrimental to the lithium intercalation/deintercalation processes. The reversible capacity of cells containing 1:1 LiPF₆/LiF₄OP in 1:1:1 EC/DEC/DMC was similar to comparable cells containing ternary electrolyte. Addition of 2% (wt) LiF₄OP to ternary electrolyte results in shorter 1.9 V plateaus but similar cycling profiles.

A solution of LiPF₆/carbonate based electrolytes has a low concentration of LiFOP when the concentration is about 0.1-5.0% (by wt). This solution when used in a rechargeabole lithium battery has increased compared to a standard lithium battery. Whereas a concentration of about 5.0-95.0% (by wt) is considered as a high concentration.

An electric current producing rechargeable Li-ion cell has an anode; a cathode; and a non-aqueous electrolyte. The non-aqueous electrolyte includes a solution of a lithium salt in a non-aqueous organic solvent containing lithium tetrafluorooxalatophosphate (LiPF₄(C₂O₄), LiF₄OP). The anode may be a lithium intercalating compound where the said lithium intercalating compound is a carbonaceous material. The cathode may be a lithium intercalating transition metal compound. The lithium intercalating transition metal compound may be selected from the group consisting of LiCoO₂; LiNiO₂; LiNi_(1−x)Co_(x)O₂ where x is 0.3<x<1.0; LiMn₂O₄; LiV₂O₅; LiM_(x)N_(1−x)O₂, where M and N are transition metals and x has a value between zero and one; LiFePO₄; LiCrS₂; and LiVS₂. The organic solvent is selected from the group consisting of organic carbonates, esters, ethers, glymes, organic nitriles and sulfones as well as mixtures thereof.

In light of the foregoing, it will now be appreciated by those skilled in the art that various changes may be made to the embodiment herein chosen for purposes of disclosure without departing from the inventive concept defined by the appended claims. 

1. A non-aqueous electrolyte for use in rechargeable lithium-ion batteries comprising a solution of LiPF₆/carbonate based electrolytes with low concentrations of LiFOP of about 0.1-5.0% by wt such that the thermal stability is increased compared to a standard lithium battery.
 2. A non-aqueous electrolyte for use in rechargeable lithium-ion batteries comprising a solution of LiPF₆/carbonate based electrolytes having high concentrations of LiFOP of about 5.0-95.0% by wt such that the thermal stability is increased compared to a standard lithium battery.
 3. A non-aqueous electrolyte for use in rechargeable lithium-ion batteries comprising a solution of LiF₄OP/carbonate based electrolytes with low or no concentrations of LiPF₆ of about 0-5.0% by wt such that the thermal stability is increased compared to a standard lithium battery.
 4. A method of making lithium tetrafluorophospahte (LiF₄C₂O₄, LiFOP) said method including: reacting PF₅ with lithium oxalate; recrystallizing from a 1:1 mixture of DMC/dichloromethane to separate LiF₄OP from LiPF₆ to form a lithium salt.
 5. An electric current producing rechargeable Li-ion cell comprising an anode; a cathode; and a non-aqueous electrolyte comprising a solution of a lithium salt in a non-aqueous organic solvent containing lithium tetrafluorooxalatophosphate (LiPF₄(C₂O₄), LiF₄OP).
 6. An electric current producing Li-ion cell according to claim 5 wherein the said anode consists of a lithium intercalating compound.
 7. An electric current producing Li-ion cell according to claim 6 wherein the said lithium intercalating compound is a carbonaceous material
 8. An electric current producing Li-ion cell according to claim 5 wherein the said cathode is a lithium intercalating transition metal compound.
 9. An electric current producing Li-ion cell according to claim 6 wherein said lithium intercalating transition metal compound is selected from the group consisting of LiCoO₂; LiNiO₂; LiNi_(1−x)Co_(x)O₂ where x is 0.3<x<1.0; LiMn₂O₄; LiV₂O₅; LiM_(x)N_(1−x)O₂, where M and N are transition metals and x has a value between zero and one; LiFePO₄; LiCrS₂; and LiVS₂.
 10. An electric current producing cell Li-ion according to claim 5 wherein said organic solvent is selected from the group consisting of organic carbonates, esters, ethers, glymes, organic nitriles and sulfones as well as mixtures thereof.
 11. A lithium salt comprising:


12. A lithium ion battery which includes: 